Preparation of esters of acids of phosphorus



Patented Apr. 5, 1949 PREPARATION OF ESTERS OF ACIDS OF PHOSPHORUS Joseph B. Dickey, Rochester, N. Y., and James G.

McNally, Oak Ridge, Tenn., assignors to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey No Drawing. Application June 29, 1945, Serial No. 602,414

. 4 Claims. (Cl. 260-461) This invention relates to the preparation of hitherto unknown esters of the acids of phosphorus and more particularly to the preparation of phosphated and phosphited compounds derived from unsaturated ketones.

This invention has as its object to provide a process for producing certain new chemical compounds which are esters of the acids of phosphorus. A further object is to provide new, phosphated and phosphitcd compounds which are derived from blown unsaturated ketones. A still further object is to provide improved phosphated and phosphited compounds having exceptional usefulness as surface-active agents, wetting, washing, and dispersing agents, and as lubricating, anti-static and conditioning agents for textile yarns, particularly those composed of or containing cellulose acetate and related cellulose derivatives. Other objects will appear hereinafter.

These objects are accomplished by the followmg invention which is based upon the unexpected discovery that if certain unsaturated ketones containing the group phorous and phosphoric acids. This is a most unusual phenomenon when itis taken into consideration that compounds containing the group such as oleic acid, butyl oleate, oleyl alcohol, carbitol oleate, ethylene glycol dioleate, and butyl ricinoleate do not add acids of phosphorus,

such as phosphorous and phosphoric acids when mixed and heated therewith.

While we do not confine ourselves to any specific theory or explanation of the mechanism of the .reaction involved when the unsaturated compounds are blown as above described, the reaction may be as follows:

tion may be represented conventionally as follows:

H H H H CC-+H0P -o-oo 4) on It will thus be seen that the phosphate or phosphito group adds to the carbon chain at the position originally occupied, before blowing, by an unsaturated linkage.

In general, the unsaturated compounds selected for blowing. such as dioleylketone, diricinoleyl k'etone, oleylmethylketone, dicrotyl ketone, succinic acid dicrotyl ketone adipic acid dioleyl ketone phenylheptadecenylic ketone, furylheptadecen- 'ylic ketone, naphthyldioleyl ketone, erucylnaphto obtain a product that'will readily react with an acid of phosphorus.

Any of the -ous or -ic acids of phosphorus may be employed for phosphating or phosphiting the blown compounds in accordance with our invention. Typical examples of such acids are phosphoric acid, metaphosphoric acid, monosodium phosphate, pyrophosphoric acid, tetraphosphoric acid, phosphorous acid, hypophosphorous acid and pyrophosphorous acid.

In view of the foregoing explanation the compounds of our invention may then be regarded as esters of acids of phosphorus prepared by reacting an -ous or -ic acid of phosphorus with a blown unsaturated ketone.;Among the unsaturated ketones which we employ in practicing our invention are those having the formula:

wherein R is an olefinically unsaturated hydrocarbon chain having 3-25 carbon atoms and R -30 hours are needed for this washed up such. as phenyl', allyi, cetyl,

limitation thereof.

Example 1 g 100 g. of dioleyllretone is blown at 150 with air using an aluminum oleate catalyst. when the specific gravity of the oily compound has increased 0.06-unit blowing is stopped. Usually step. when cool add. 50 g. of 85% phosphoric acid and heat with stirring on .a water bath for 10-12 hours. The excess acid is removed with cold water or cold dilute salt water. The heavy viscous brown colored product is soluble in water.

Example 2 Example 3 100 g. of dicrotyl ketone is blown using copper naphthenate until the viscosity has increased 0.06tunit; The product is phosphated and using cold dilute salt solution to remove the excess acid. It is water soluble.

Example 4 100g. succinic acid dicrotyl ketone is blown at 150 C. until the specific gravity changes about 0.075 units and the resulting heavy oil is reacted with 50 g. 85% phosphoric acid as in the previous examples. The acid is water soluble and readily forms salts with various inorganic bases.

While we have found it convenient to illustrate our invention by reference to procedures involving the blowing of certain specific unsaturated ketones, it will be evident that many modifications in such procedures may be made within the scope of our invention. In general, it may be said that, irrespective of the particular ketone dealt with, the blowing operation may be carried out in a manner analogous to that which is customarily employed in the blowing of various oils, fats, and waxes.

The blown and phosphated or phosphited compounds of our invention have many valuable applications in industry. For example, they may and organic radical which may contain an e e h l n mun.

.oleyl, etc.

be employed as surface-active. agents, wetting. washing and dispersing agents. We have also found them to have outstanding properties when employed as lubricating anti-static and conditioning agents for textile yarns, particularly those composed of or containing cellulose acetate and related cellulose derivatives.

What we claim is:

1. Ihe process of producing an ester of an acid of phosphorous which .comprises blowing an unsaturated ketone having the formula:

wherein R is an unsaturated hydrocarbon chain of 3 to 25 carbon atoms in which the unsaturation is limited to olefinlc unsaturation and R is a hydrocarbon radical, at from to 200 C., until an appreciable increase in specific gravity occurs, and thereafter treating the blown ketone with an acid of phosphorous selected from the group consisting of phosphoric and phosphorous acids.

2. The process of producing an ester of an acid of phosphorus which comprises blowing dioleyl ketone, at from 50 to 200 C., until an appreclable increase in specific gravity occurs, and

thereafter treating the blown ketone with phos- I phoric acid. 7 I

3. The process of producing an ester of an acid of phosphorus which comprises blowing oleyl methyl ketone, at from 50 to 200 C., until an appreciable increase in specific gravity occurs, and thereafter treating the blown ketone with a mixture of phosphoric and phosphorous acids.

4. The process of producing an ester of an acid of phosphorus which comprises blowing succinic acid dicrotyl ketone, at from 50 to 200 0., until an appreciable increase in specific gravity occurs,

.and thereafter treating the blown ketone with phosphoric acid.

JOSEPH B. DICKEY. JAMES G. McNALLY.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Great Britain Aug. 24, 1938 

